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Isomer-Specific Product Detection of Gas-Phase Xylyl Radical Rearrangement and Decomposition Using VUV Synchrotron Photoionization

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Isomer-Specific Product Detection of Gas-Phase Xylyl Radical Rearrangement and Decomposition Using VUV Synchrotron Photoionization University of Wollongong Research Online Faculty of Science, Medicine and Health - Papers: part A Faculty of Science, Medicine and Health 1-1-2014 Isomer-specific product detection of gas-phase xylyl radical rearrangement and decomposition using VUV synchrotron photoionization Patrick Hemberger Paul Scherrer Institute Adam J. Trevitt University of Wollongong, [email protected] Thomas Gerber Paul Scherrer Institute Edward Ross University of Melbourne Gabriel da Silva University of Melbourne, [email protected] Follow this and additional works at: https://ro.uow.edu.au/smhpapers Part of the Medicine and Health Sciences Commons, and the Social and Behavioral Sciences Commons Recommended Citation Hemberger, Patrick; Trevitt, Adam J.; Gerber, Thomas; Ross, Edward; and da Silva, Gabriel, "Isomer-specific product detection of gas-phase xylyl radical rearrangement and decomposition using VUV synchrotron photoionization" (2014). Faculty of Science, Medicine and Health - Papers: part A. 1781. https://ro.uow.edu.au/smhpapers/1781 Research Online is the open access institutional repository for the University of Wollongong. For further information contact the UOW Library: [email protected] Isomer-specific product detection of gas-phase xylyl radical rearrangement and decomposition using VUV synchrotron photoionization Abstract Xylyl radicals are intermediates in combustion processes since their parent molecules, xylenes, are present as fuel additives. In this study we report on the photoelectron spectra of the three isomeric xylyl radicals and the subsequent decomposition reactions of the o-xylyl radical, generated in a tubular reactor and probed by mass selected threshold photoelectron spectroscopy and VUV synchrotron radiation. Franck-Condon simulations are applied to augment the assignment of elusive species. Below 1000 K, o- xylyl radicals decompose by hydrogen atom loss to form closed-shell o-xylylene, which equilibrates with benzocyclobutene. At higher temperatures relevant to combustion engines, o-xylylene generates styrene in a multistep rearrangement, whereas the p-xylylene isomer is thermally stable, a key point of difference in the combustion of these two isomeric fuels. Another striking result is that all three xylyl isomers can generate p-xylylene upon decomposition. In addition to C8H8 isomers, phenylacetylene and traces of benzocyclobutadiene are observed and identified as further reaction products of o-xylylene, while there is also some preliminary evidence for benzene and benzyne formation. The experimental results reported here are complemented by a comprehensive theoretical C8H8 potential energy surface, which together with the spectroscopic assignments can explain the complex high-temperature chemistry of o-xylyl radicals. Keywords GeoQuest Disciplines Medicine and Health Sciences | Social and Behavioral Sciences Publication Details Hemberger, P., Trevitt, A. J., Gerber, T., Ross, E. & da Silva, G. (2014). Isomer-specific product detection of gas-phase xylyl radical rearrangement and decomposition using VUV synchrotron photoionization. The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 118 (20), 3593-3604. This journal article is available at Research Online: https://ro.uow.edu.au/smhpapers/1781 Isomer-Specific Product Detection of Gas-Phase Xylyl Radical Rearrangement and Decomposition using VUV Synchrotron Photoionization Patrick Hemberger,a) * Adam J. Trevitt,b) T. Gerber,a) Edward Ross, c) Gabriel da Silva c) a) Molecular Dynamics Group, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland b) School of Chemistry, University of Wollongong, New South Wales 2522, Australia c) Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010, Australia KEYWORDS Methylbenzyl radical, combustion, fuel additives, xylenes, benzyl radical, styrene 1 ABSTRACT: Xylyl radicals are known intermediates in combustion processes since their parent molecules, xylenes, are present as fuel additives. In this study we report on the photoelectron spectra of the three isomeric xylyl radicals and the subsequent decomposition reactions of the o-xylyl radical, generated in a tubular reactor and probed by mass selected threshold photoelectron spectroscopy and VUV synchrotron radiation. Franck Condon simulations are applied to augment the assignment of elusive species. Below 1000 K, o-xylyl radicals decompose by hydrogen atom loss to form closed-shell o-xylylene, which equilibrates with benzocyclobutene. At higher temperatures relevant to combustion engines, o-xylylene generates styrene in a multi-step rearrangement, whereas the p-xylylene isomer is thermally stable, a key point of difference in the combustion of these two isomeric fuels. Another striking result is that all three xylyl isomers can generate p-xylylene upon decomposition. In addition to C8H8 isomers, phenylacetylene and traces of benzocyclobutadiene are observed and identified as further reaction products of o- xylylene, while there is also some preliminary evidence for benzene and benzyne formation. The experimental results reported here are complemented by a comprehensive theoretical C8H8 potential energy surface, which together with the spectroscopic assignments can explain the complex high-temperature chemistry of o-xylyl radicals. 2 1) Introduction Aromatic hydrocarbons are widely used in fuels as additives due to their high energy densities and octane ratings. In order to reduce harmful benzene emissions, fuel compositions are now typically regulated to contain less than 1 %vol benzene, and from 2013 the US regulated the total amount to a maximum of 0.62 %vol.1 In order to increase anti-knock properties of gasoline, whilst reducing benzene emissions, toluene and other polyalkylated benzenes (e.g. xylenes, trimethyl benzenes, ethylbenzene) are used instead. Since these species can form radicals more readily than benzene (sp3 vs. sp2 hybridized C-H bonds and the stability of corresponding radicals), and because the resultant benzylic radicals are generally unreactive towards O2, an increased variety of side reactions can occur that may lead to the formation of polycyclic aromatic hydrocarbon (PAH) molecules, the precursors of soot. Experimental and theoretical investigations revealed that toluene pyrolysis leads mostly to the formation of benzyl radicals, which can decompose further by hydrogen atom loss to yield the five-membered ring 2-5 fulvenallene (C7H6). In 2009 it was found that a subsequent hydrogen abstraction could lead to fulvenallenyl radical (the global C7H5 minimum), which was unambiguously identified by measuring its mass-selected threshold photoelectron spectrum (ms-TPES).6-8 The products arising from the dissociation of substituted benzyl radicals, however, are less well understood. 3 CH3 CH2 CH2 H3C H3C H2C DT CH3 CH2 CH2 DT H3C H3C H2C CH3 CH2 CH2 DT CH3 CH3 CH2 Scheme 1 Putative decomposition pathways of xylenes. The decomposition dynamics of xylenes are also relatively unexplored, despite their prevalence in gasoline. It is generally accepted that the first xylene decomposition step is C-H bond fission at a methyl group yielding the corresponding xylyl (methylbenzyl) radical9-10 (Scheme 1) but further unimolecular reactions have not been extensively studied. Possible decomposition products are the corresponding xylylenes, which appear after hydrogen abstraction (Scheme 1). While the ortho and the para isomers possess a closed shell character, meta-xylylene exists as a biradical, resulting in a structure that is 40-45 kcal/mol less stable than the ortho and para isomers. In 1955 Farmer et al. investigated the three xylyl radicals by electron impact mass spectrometry (EI-MS) and their results suggested that the meta isomer does not decompose to form m-xylylene but rather one of the other two xylylene isomers.11 In more recent times, a few studies have reported on xylene and xylyl radical decomposition. Shock tube experiments revealed that o- and p-xylyl radicals decompose faster than the m-xylyl radical and it was 4 assumed that the triplet m-xylylene does play an important role.12 Farrell et al. observed a reduced burning velocity of m-xylyene compared to the ortho and para isomers and attributed this effect to the enhanced stability of m-xylyl radicals.13 In 2009 it was predicted that m-xylyl preferably rearranges to p-xylyl and subsequently loses a hydrogen atom to yield p-xylylene via a maximum barrier of 70 kcal mol-1, whereas the decomposition to m-xylylene and 3- methylfulvenallene must surmount 109 and 87 kcal mol-1 barriers, respectively.10 Since the first study by Farmer et al. it took almost 60 years until this hypothesis could be proven spectroscopically,14 with a recent study conclusively identifying p-xylylene as the dominant stable product of m-xylyl radical pyrolysis. Different from the meta case, the ortho and para xylyl radicals are widely assumed to decompose to their corresponding xylylenes, though this has not yet been demonstrated unequivocally. Moreover, there have been surprisingly few theoretical15 and experimental16,17 investigations carried out on the further rearrangement and decomposition processes of the xylylenes and other C8H8 isomers. Using VUV photoionization techniques, coupled with a heated reactor source to selectively produce xylyl radical isomers, it is possible to intercept decomposition products by mass- selected threshold photoelectron spectroscopy (ms-TPES). We have shown that the imaging photoelectron photoion
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